TWI401274B - Novel high polymer and copolymer and method of making the same - Google Patents

Description

Novel high molecular polymer and copolymer and preparation method thereof

The present invention relates to a polymer, and more particularly to a polymer having a bistriphenylamine functional group.

Electroluminescent devices are now replacing, for example, so-called incandescent lamps, gas-filled lamps, and are attracting attention in the use of large-area solid state light sources. On the other hand, in the field of flat panel display (PFD), the most powerful self-luminous display that can replace the liquid crystal display has also attracted attention. In particular, an organic electroluminescent (EL) element which uses an organic material to constitute a component material, such a low-power type full color flat panel display (FPD), is moving toward commercialization. In particular, there are also polymer-type organic excitation light (EL) elements which use polymer materials to form organic materials, compared with low-molecular organic excitation light (EL) elements which must be formed in a vacuum system, because It is an indispensable component for large-screen organic excitation light (EL) displays in the future, such as printing, inkjet (ink-jet), and the like.

Heretofore, in a polymer type organic excitation light (EL) device, any one of a conjugation polymer such as polyphenylene-vinylene and a non-conjugated polymer can be used. Polymer material. However, the low luminescence lifetime of components has become an obstacle to the construction of full color displays.

In order to solve the above problems, in recent years, although a polymer type organic excitation light (EL) element using various conjugated polymers of a p-phenylene type has been proposed, it has not been found in terms of stability. Satisfied. Therefore, there is still a need for an organic excitation light element material that can solve the above problems.

In order to solve the above problems of the conventional organic excitation light element material, the present invention provides a novel high molecular polymer and a copolymer and a preparation method thereof.

In one aspect, the present invention discloses a high molecular polymer, the monomer comprising a bistriphenylamine functional group comprising a first end and a second end; a hydrazine functional group bonded to the first end; And at least a diphenyl isopropyl group bonded to the second end.

In another aspect, the present invention discloses a high molecular polymer comprising the structural unit of the following formula (II)

Wherein R is C ₈ H ₁₇ ~ C ₁₂ H ₂₅ and n is 5-30.

In still another aspect, the present invention discloses a high molecular copolymer comprising a structural unit of the following formula (III)

Wherein R is C ₈ H ₁₇ ~ C ₁₂ H ₂₅ , x is 0.05 to 0.15, y is 0.95 to 1.05, and z is 0.85 to 0.95.

In still another aspect, the present invention discloses a method for preparing a high molecular polymer comprising a preliminary dibromobenzene compound, a bismuth borate compound, an aqueous potassium carbonate solution, and a toluene solution, and placed in a reaction bottle through which nitrogen is passed; Tetrakis(triphenylphosphine)palladium is added to the above reaction flask and heated to a first predetermined temperature and refluxed for a first predetermined time; the above polymer is precipitated in a methanol solution and filtered, and the above polymer is washed with a large amount of water. And heating the above polymer to a second predetermined temperature under vacuum and drying for a second predetermined time.

In still another aspect, the present invention discloses a method for preparing a polymer copolymer comprising a preliminary bisbromobenzene compound, a bismuth borate compound, a dibromothiophene compound, an aqueous potassium carbonate solution, and a toluene solution, and is placed in a nitrogen-passing solution. In the reaction flask; adding tetrakis(triphenylphosphine)palladium to the above reaction flask and heating to a first predetermined temperature and refluxing for a first predetermined time; precipitating the above polymer copolymer in methanol solution and filtering it in a large amount Water rinsing the above polymer copolymer; and heating the polymer copolymer to a second predetermined temperature under vacuum and drying for a second predetermined time.

One of the advantages of the present invention is that the high molecular polymer and the copolymer of the present invention have good solubility, heat resistance, high carrier fluidity, and low ionization potential.

Another advantage of the present invention is that the high molecular polymers and copolymers of the present invention have good optical properties and properties of the electron donor.

Still another advantage of the present invention is that the ultraviolet/visible spectrum (UV-vis) absorption wave of the polymer copolymer of the present invention shifts to a long wavelength, which can increase the absorption efficiency.

These and other advantages will be apparent to the reader from the following description of the preferred embodiments.

The present invention will be described in terms of the preferred embodiments and aspects of the invention, which are intended to be illustrative and not restrictive. Therefore, the present invention may be widely practiced in other embodiments in addition to the preferred embodiments described in the specification.

The present invention provides a novel high molecular polymer having a triphenylamine functional group and a hydrazine functional group, and a novel polymer copolymer having a triphenylamine functional group, a hydrazine functional group, and a thiophene-functional group, and Preparation. Since the novel high molecular polymer and the copolymer have triphenylamine functional groups, they have good solubility, heat resistance, carrier mobility and low ionization potential, and are easy to be used. The film is formed, and its central nitrogen atom has redox ability and can be applied to an electrochromic material, so it can be applied to a building glass, an indicator, an electrochromic display, a smart window, and the like. Moreover, since the central nitrogen atom of the triphenylamine functional group of the novel high molecular polymer and the copolymer is easily oxidized and loses electrons, it can be applied to a hole-transporting material, and thus can be applied to a thin layer material such as organic. Light-emitting diodes, solar cells, photoreceptors, illuminants, electroluminescent elements, and the like. Since the novel high molecular polymers and copolymers described above have an oxime functional group, they have good optical properties and properties of an electron donating group. In addition, since the novel polymer copolymer has a thiophene-containing group, the ultraviolet/visible spectrum (UV-vis) absorption wave shifts to a long wavelength and the absorption efficiency increases, and can be applied to the field of solar cells.

The novel high molecular polymer and the preparation method of the copolymer of the present invention involve bis[4-(2-phenyl-2-propyl)phenyl]nitrobenzene compound (BPPAN), two [4-(2) -Phenyl-2-propyl)phenyl]aminobenzene compound (BPPAA) and bis[4-(2-phenyl-2-propyl)phenyl]dibromobenzene compound (BPPADIBr), and utilizes [4-(2-Phenyl-2-propyl)phenyl]dibromobenzene compound (BPPADIBr) is synthesized with a bismuth borate compound by Suzuki coupling reaction to synthesize a novel polymer, or [4-(2-Phenyl-2-propyl)phenyl]dibromobenzene compound (BPPADIBr) is copolymerized with a lanthanum borate compound and dibromothiophene to synthesize a novel polymer copolymer.

I. Nitrobenzene compound

The present invention proposes a bis[4-(2-phenyl-2-propyl)phenyl]nitrobenzene compound (BPPAN) as shown in the formula (1).

Next, an example will be given to illustrate the synthetic preparation method of BPPAN, and to confirm and analyze the chemical structure of the obtained compound.

First, 49 millimoles of bis[4-(2-phenyl-2-propyl)phenylamine, 49 millimoles of 1-fluoro-4-nitrobenzene, 49 millimolar of sodium hydride (Sodium) The hydride) and 120 ml of Dimethyl sulfoxide are placed in a reaction flask and reacted at 115 to 125 ° C, preferably 120 ° C for 48 hours. Thereafter, the cooled reaction mixture was precipitated in methanol. Then, the solid obtained was subjected to column chromatography to obtain n-hexane:methylene chloride (n-Hexane: Dichloromethane) = 2:1 to obtain a yellow solid (BPPAN). The nitro compound (BPPAN) had a melting point of 150-151 ° C and a yield of 50%.

The synthetic reaction formula of the above dinitrogen compound (BPPAN) is as follows:

Further, the obtained nitrobenzene compound (BPPAN) was identified by ¹ H-NMR analysis, ¹³ C-NMR analysis, and elemental analysis of a nuclear magnetic resonance spectrum (NMR spectrum). In the table of the obtained NMR spectrum, s refers to a singlet (Singlet), d refers to a doublet (Doublet), t refers to a triplet (Triplet), q refers to a quartet (Quartet), and m refers to a multiplet (Multiplet).

¹ H NMR. (CDCl ₃ ): δ (ppm) = 8.05-8.08 (d, 1H); 7.37-7.38 (d, 2H); 7.35-7.36 (t, 2H); 7.28-7.30 (d, 2H); 7.24-7.27 (m, 1H); 7.12-7.14 (d, 2H); 6.93-6.95 (d, 1H); 1.78 (s, 6H).

¹³ C NMR (CDCl ₃ ): δ (ppm) = 153.46, 150.01, 148.26, 142.80, 139.62, 128.13, 128.03, 126.62, 125.88, 125.71, 125.31, 117.42, 42.62, 30.65.

Elemental analysis:

The theoretical value is: C, 82.10%; H, 6.51%; N, 5.32%;

Analytical values were: C, 81.67%; H, 6.39%; N, 5.21%.

II. Aminobenzene compounds

The aminobenzene compound of the present invention is bis[4-(2-phenyl-2-propyl)phenyl]aminobenzene compound (BPPAA) (Bis[4-(2-phenyl-2-propyl)phenyl]phenylamine) ), which is as shown in equation (2).

Formula (2)

Next, an example will be given to explain the production method of BPPAA, and to confirm and analyze the chemical structure of the obtained compound.

First, 33.46 mmol of nitro compound (BPPAN) monomer, 0.3 g of 10% activated carbon palladium (Pd/C) and 200 ml of ethanol were placed in the reaction flask. Then, it warmed to 85 ~ 95 ℃, preferably 90 ℃, was slowly added 10 ml of hydrazine _{(H 2 NNH 2 ‧H 2 O} ). After the addition of the hydrazine, the reaction was carried out for 24 hours, and after completion of the reaction, filtration was carried out to remove 10% of activated carbon palladium (Pd/C), and a filtrate was obtained. After the filtrate obtained was cooled and precipitated, it was filtered again to obtain a solid portion. Then, the obtained solid was recrystallized twice from ethanol to obtain a white amine-based compound, which was dried under vacuum. The amine compound (BPPAA) had a melting point of 107-108 ° C and a yield of 60%.

The synthetic reaction formula of the above amine compound (BPPAA) is as follows:

Further, the obtained amine-based compound (BPPAA) was identified by ¹ H-NMR analysis, ¹³ C-NMR analysis, and elemental analysis of a nuclear magnetic resonance spectrum (NMR spectrum).

¹ H NMR. (DMSO-d ₆ ): δ (ppm) = 7.20-7.21 (d, 2H); 7.19-7.20 (d, 2H); 7.09-7.12 (m, H); 6.98-7.00 (d, 2H) 6.79 (d, 2H); 6.77 (d, 2H); 6.56-6.58 (d, 1H); 5.02 (s, 1H); 1.57 (s, 6H).

¹³ C NMR (DMSO-d ₆ ): δ (ppm) = 150.3, 145.9, 145.4, 142.5, 135.2, 125.3, 127.9, 127.8, 126.9, 126.2, 125.3, 120.73, 114.9, 41.7, 30.3.

Elemental analysis:

Theoretical values: C, 87.05%; H, 7.31%; N, 5.64%;

Analytical values were: C, 86.9%; H, 7.13%; N, 5.61%.

III. Dibromo compound

The bisbromobenzene compound of the present invention is bis[4-(2-phenyl-2-propyl)phenyl]dibromobenzene compound (BPPADIBr) (Bis[4-(2-phenyl-2-propyl)phenyl) ]phenyldibromide), as shown in formula (3).

Next, an example will be given to illustrate the production method of BPPADIBr, and to confirm and analyze the chemical structure of the obtained compound.

First, 14 mmoles of 1-bromo-4-iodobenzene, 6 mM of bis[4-(2-phenyl-2-propyl)phenyl]aminobenzene compound (BPPAA), 0.36 m Mole's tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ), 0.72 mmol of bisdiphenylphosphinoferrocene (DPPF), 27 mmoles of third butanol ( Sodium tert-butoxide and 10 ml of water-removed toluene were placed in a 250 ml three-neck reaction flask, and a condenser was placed, and heated under reflux to a reflux temperature for 6 hours under nitrogen. After the reaction, the toluene solvent was removed, and the organic phase was extracted with dichloromethane and water, dried over magnesium sulfate, filtered, and then evaporated, and then purified by column chromatography, toluene: n-hexane = 1:4. Recrystallization from ethyl acetate gave a white dibromo compound. The melting point of this dibromo compound was 225 °C.

The synthetic reaction formula of the above dibromo compound (BPPADIBr) is as follows:

Further, the obtained dibromo compound (BPPADIBr) was identified by ¹ H-NMR analysis, ¹³ C-NMR analysis and elemental analysis of a nuclear magnetic resonance spectrum (NMR spectrum). In the table of the obtained NMR spectrum, s refers to a singlet (Singlet), d refers to a doublet (Doublet), t refers to a triplet (Triplet), q refers to a quartet (Quartet), and m refers to a multiplet (Multiplet).

¹ H NMR. (CDCl ₃ ): δ (ppm)=1.71 (s, 12H,); 6.92-6.97 (m, 4H,); 6.99-7.01 (m, 6H,); 7.12-7.13 (d, 4H, 7.18-7.22 (m, 2H,); 7.30-7.32 (d, 8H,); 7.34-7.36 (d, 4H,), as shown in the first a diagram and the first b diagram.

¹³ C NMR (DMSO-d ₆ ): δ (ppm) = 30.7, 42.5, 114.9, 123.4, 124.7, 124.8, 125.6, 125.9, 126.73, 127.5, 128.0, 132.2, 140.9, 144.1, 144.9, 145.0, 146.6, 150.6 , as shown in the second a diagram and the second b diagram. The third graph shows the two-dimensional correlation spectrum (2D-COSY) of bis[4-(2-phenyl-2-propyl)phenyl]dibromobenzene compound (BPPADIBr). The fourth graph shows the two-dimensional heteronuclear multi-quantum correlation spectroscopy (2D-HMQC) of bis[4-(2-phenyl-2-propyl)phenyl]dibromobenzene compound (BPPADIBr).

Elemental analysis:

Theoretical values: C: 71.47; H: 5.25; N: 3.47%;

Analytical values were: C: 72.05; H: 5.30; N: 3.09%.

IV. Poly(4-(2-phenyl-2-propyl)phenyl]-bisoctadecyl (Poly(BPPAFL8))

The polymer of the present invention has a structure represented by the formula (5). This material is obtained by subjecting a dibromo compound (BPPADIBr) represented by the above formula (3) and a boric acid compound represented by the formula (4) to a Suzuki coupling reaction as a monomer.

Formula (4) 9,9-dioctylindole-2,7-diboronic acid di(1,3-propanediol) or 9,9-didodecylindole-2,7-diboronic acid di(1,3 - Propylene glycol) ester wherein R is C ₈ H ₁₇ ~ C ₁₂ H ₂₅ , preferably C ₈ H ₁₇ or C ₁₂ H ₂₅ .

Poly(2-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)) and polydi[4-(2-phenyl-2-propyl) Phenyl]-dodedodecyl) (Poly(BPPAFL12)), wherein R is C ₈ H ₁₇ ~ C ₁₂ H ₂₅ , preferably C ₈ H ₁₇ or C ₁₂ H ₂₅ , and n is 5-30.

As shown in the formula (5), in one embodiment, the present invention discloses a high molecular polymer, the monomer comprising a bistriphenylamine functional group comprising a first end and a second end; a fluorene functional group a group bonded to the first end; and at least a diphenyl isopropyl group bonded to the second end.

[Example 1]

Synthesis of Poly(4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ )

As shown in the eleventh figure, in step 101, 0.92 mmol of dibromo compound (BPPADIBr), 0.92 mmol of boronic acid (9,9-dioctylindole-2,7-diborate di(II) 1,3-propanediol), 0.918 ml of 2M aqueous potassium carbonate solution (K ₂ CO ₃ (aq)), and 20 ml of toluene (Toluene) were placed in a nitrogen-containing reaction flask. Thereafter, in step 102, 0.6 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) is added, and the mixture is heated to 100 to 110 ° C, preferably 105 ° C, and refluxed. hour. Then, in step 103, the polymer solution is precipitated in one liter of a methanol solution. The product obtained by filtering the solution was washed with a large amount of water, then dissolved in toluene, and precipitated in one liter of a methanol solution, and repeated three times. Next, in step 104, it is further heated to 145-155 ° C under vacuum, preferably at 150 ° C for 24 hours, and the yield is 92%.

¹ H-NMR of the obtained poly([4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)) by nuclear magnetic resonance spectrum (NMR spectrum) Analysis and ¹³ C-NMR analysis were performed for identification. The fifth figure shows gel permeation chromatography (GPC; Gel Permeation Chromatography) of poly(4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ ) ) Figure.

¹ H NMR. (CDCI ₃ ): δ (ppm) = 0.75 (4H); 0.79-0.82 (6H); 1.08-1.22 (20H,); 1.68 (12H,); 2.05 (4H); 7.03-7.06 (4H) 7.11 (4H); 7.17-7.20 (4H); 7.26 (2H); 7.28-7.30 (8H); 7.57-7.60 (8H); 7.75-7.77 (2H).

¹³ C NMR (CDCl ₃ ): δ (ppm) = 14.06, 22.59, 23.82, 25.61, 29.21, 29.22, 30.05, 30.77, 31.78, 40.50, 42.47, 55.21, 67.96, 119.88, 120.90, 123.15, 123.69, 125.22, 125.49 , 125.55, 125.90, 126.77, 127.49, 127.78, 127.97, 135.48, 139.36, 139.74, 144.70, 145.29, 146.93, 150.75, 151.63.

Determination of poly(4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ ) by thermal gravimetric analysis under air The 10% thermal cracking temperature (T _d10 ) is 430-440 ° C, preferably 435 ° C, and the nitrogen cracking temperature (T _d10 ) under nitrogen (Nitrogen) is 445-460 ° C, preferably 453 °C; and the glass transition temperature measured at a nitrogen flow rate of 10 c.c./min is 130 to 145 ° C, preferably 137 ° C, as shown in the sixth and seventh figures.

Ultraviolet light (UV) of poly(4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ ) in tetrahydrofuran (THF) solution The absorption peaks are 313 and 382 nm (nm), and the photoexcitation fluorescence spectrum (PL; photoluminescence) peak is 612 nm (nm); while the solid-state ultraviolet (UV) absorption peak is 319 and 386 nm (nm) The photoexcitation fluorescence spectrum (PL; photoluminescence) peak is 528 nm (nm), as shown in the eighth and ninth diagrams.

The polymer material also has electrochemical properties, and is studied by cyclic voltammetry (CV). After adding cycloferradienyl iron (ferrocene) and cyclopentadienyl iron ion (ferrocenenium), the oxidation potential is equivalent to 4.8 eV (eV) in a vacuum environment, and the conjugated polymer can be calculated. The highest occupied molecular orbital (HOMO) energy level. Therefore, the lowest unoccupied molecular orbital (LUMO) can be calculated by the following formula: LUMO=HOMO+E _g . The highest occupied molecular orbital domain of poly(4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ ) under tetrahydrofuran (THF) The values of HOMO) and the lowest empty molecular orbital (LUMO) are calculated as -4.93 and -1.22 electron volts (eV), respectively, as shown in the tenth figure.

V. Copolymer of bis[4-(2-phenyl-2-propyl)phenyl]-bisoctadecyl and 2,5-dibromothiophene

The polymer of the present invention has a structure represented by the formula (7), which is a dibromo compound (BPPADIBr) represented by the above formula (3), and a boric acid compound represented by the formula (4), and a formula The monomer of (6) is obtained by copolymerization in different proportions.

A copolymer of bis[4-(2-phenyl-2-propyl)phenyl]-bisoctadecyl and 2,5-dibromothiophene of formula (7).

In one embodiment, C ₈ in the formula (7) may also be any one of C ₉ to C ₁₂ , and 0.1 in the formula (7) may also be any one of 0.05 to 0.15, in the formula (7) 1 may be any one of 0.95 to 1.05, and 0.9 of the formula (7) may be any of 0.85 to 0.95.

[Example 2]

Synthesis of a copolymer of bis[4-(2-phenyl-2-propyl)phenyl]-bisoctadecyl and 2,5-dibromothiophene

As shown in Fig. 12, in step 201, 0.0895 mmol of dibromo compound (BPPADIBr) and 0.8955 mmol of lanthanum borate (9,9-dioctylindole-2,7-diborate di 1,3-propanediol), 0.806 mmol of 2,5-dibromothiophene, 2 ml of 3M aqueous potassium carbonate solution (K ₂ CO ₃ (aq)), and 4 ml of toluene (Toluene) was placed in a nitrogen-containing reaction flask. Thereafter, in step 202, 3 millimoles of tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) is added, and the mixture is heated to 100 to 110 ° C, preferably 105 ° C, and refluxed. hour. Then, in step 203, the polymer solution is precipitated in one liter of methanol solution, and the product obtained by filtering the solution is washed with a large amount of water, then dissolved in toluene, and precipitated in one liter of methanol solution, and repeated three times. . Next, in step 204, it is further heated to 145 to 155 ° C under vacuum, preferably at 150 ° C for 24 hours.

a copolymer of bis[4-(2-phenyl-2-propyl)phenyl]-bisoctadecyl and 2,5-dibromothiophene (POLY(DITPATH8)) in tetrahydrofuran (THF) solution The ultraviolet (UV) absorption peak is 430 nm (nm), the photoexcited fluorescence spectrum (PL; photoluminescence) peak is 611 nm (nm), and the solid-state ultraviolet (UV) absorption peak is 430 nm ( Nm), the photoexcited fluorescence spectrum (PL; photoluminescence) peak is 533 nm (nm), as shown in the eighth and ninth.

The above description is a preferred embodiment of the invention. Those skilled in the art should be able to understand the invention and not to limit the scope of the patent claims claimed herein. The scope of patent protection is subject to the scope of the patent application and its equivalent fields. Any modification or refinement made by those skilled in the art without departing from the spirit or scope of the present invention is equivalent to the equivalent change or design made in the spirit of the present disclosure, and should be included in the following patent application scope. Inside.

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The invention can be understood by the following description of the preferred embodiments and the detailed description and the accompanying drawings. The same reference numerals in the drawings refer to the same elements in the present invention. However, it is to be understood that the preferred embodiments of the invention are intended to be

The first a diagram and the first b diagram are ¹ H-NMR spectrum of bis[4-(2-phenyl-2-propyl)phenyl]dibromobenzene compound (BPPADIBr) according to an embodiment of the present invention. .

2A and 2b are ¹³ C-NMR spectra of bis[4-(2-phenyl-2-propyl)phenyl]dibromobenzene compound (BPPADIBr) according to an embodiment of the present invention. .

The third a and third b diagrams are 2D-COSY spectra of bis[4-(2-phenyl-2-propyl)phenyl]dibromobenzene compounds (BPPADIBr) according to an embodiment of the present invention.

The fourth and fourth b-pictures are 2D-HMQC spectra of bis[4-(2-phenyl-2-propyl)phenyl]dibromobenzene compounds (BPPADIBr) according to an embodiment of the present invention.

The fifth figure is a gel permeation of poly(4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ ) according to an embodiment of the present invention. Chromatography (GPC) chart.

The sixth figure is a differential scanning heat of poly(4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ ) according to an embodiment of the present invention. Differential Scanning Calorimetry (DSC) map.

Figure 7 is a thermogravimetric analysis of poly(4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ ) according to an embodiment of the present invention. (TGA) map.

The eighth figure is a poly([4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ ) and two [4] according to an embodiment of the present invention. UV/vis spectrum (UV-vis) of a copolymer of (2-phenyl-2-propyl)phenyl]-bisoctadecyl and 2,5-dibromothiophene (POLY(DITPATH8)) .

The ninth diagram is a poly([4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ ) and two [4] according to an embodiment of the present invention. Photoexcited fluorescence spectrum (PL) of a copolymer of (2-phenyl-2-propyl)phenyl]-bisoctadecyl and 2,5-dibromothiophene (POLY (DITPATH8)).

The tenth graph is a cyclic voltammetry of poly(4-(2-phenyl-2-propyl)phenyl]-bisoctadecene (Poly(BPPAFL8)C ₈ H ₁₇ ) according to an embodiment of the present invention. (CV) map.

The eleventh drawing is a flow chart showing the steps of a method for preparing a high molecular polymer according to an embodiment of the present invention.

Figure 12 is a flow chart showing the steps of a method for preparing a polymer copolymer according to an embodiment of the present invention.

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Claims (30)

a high molecular polymer comprising: a bis-triphenylamine functional group comprising a first end and a second end; a fluorene functional group bonded to the first end; and at least diphenyl a isopropyl group bonded to the second end. The high molecular polymer according to claim 1, wherein the oxime functional group is as shown in the formula (I) Wherein R is C ₈ H ₁₇ ~C ₁₂ H ₂₅ . The polymer according to claim 1, wherein the polymer has a 10% thermal cracking temperature of 430 to 440 ° C under air. The polymer according to claim 1, wherein the polymer has a 10% thermal cracking temperature of 445 to 460 ° C under nitrogen. The high molecular polymer according to claim 1, wherein the high molecular weight polymer has a glass transition temperature of 130 to 145 °C. The high molecular polymer according to claim 1, wherein the high molecular weight polymer has a UV (UV) absorption peak of 313 and 382 nm (nm) in a tetrahydrofuran (THF) solution. The high molecular polymer according to claim 1, wherein the photoexcited fluorescence spectrum (PL) peak of the high molecular polymer in tetrahydrofurfuryl (THF) solution is 612 nm (nm). The high molecular polymer according to claim 1, wherein the high molecular weight ultraviolet (UV) absorption peak of the high molecular polymer is 319 and 386 nm (nm). The high molecular polymer according to claim 1, wherein the high molecular weight polymer excitation fluorescence spectrum (PL) peak in the solid state is 528 nm (nm). The polymer according to claim 1, wherein the polymer has an oxidation potential of 4.8 eV. The high molecular polymer according to claim 1, wherein the highest occupied molecular orbital domain of the high molecular polymer is -4.93 electron volts (eV). The high molecular polymer according to claim 1, wherein the lowest molecular molecular domain of the high molecular polymer is -1.22 electron volts (eV). A high molecular polymer comprising the structural unit of the following formula (II) Wherein R is C ₈ H ₁₇ ~ C ₁₂ H ₂₅ and n is 5-30. The high molecular polymer according to claim 13, wherein the high molecular polymer has a 10% thermal cracking temperature of 430 to 440 ° C under air. The high molecular polymer according to claim 13, wherein the high molecular polymer has a 10% thermal cracking temperature of 445 to 460 ° C under nitrogen. The polymer according to claim 13, wherein the polymer has a glass transition temperature of 130 to 145 °C. The high molecular polymer according to claim 13, wherein the high molecular weight polymer has a UV (UV) absorption peak of 313 and 382 nm (nm) in a tetrahydrofurfuryl (THF) solution. The high molecular polymer according to claim 13, wherein the photopolymerization fluorescence spectrum (PL) peak of the high molecular polymer in tetrahydrofurfuryl (THF) solution is 612 nm (nm). The high molecular polymer according to claim 13, wherein the high molecular weight ultraviolet (UV) absorption peak of the high molecular polymer is 319 and 386 nm (nm). The high molecular polymer according to claim 13, wherein the high molecular weight photoexcited fluorescence spectrum (PL) peak of the high molecular polymer is 528 nm (nm). The polymer according to claim 13, wherein the polymer has an oxidation potential of 4.8 eV. The high molecular polymer of claim 13, wherein the highest molecular molecular domain of the high molecular polymer is -4.93 electron volts (eV). The high molecular polymer of claim 13, wherein the lowest molecular molecular domain of the high molecular polymer is -2.22 electron volts (eV). A high molecular copolymer comprising a structural unit of the following formula (III) Wherein R is C ₈ H ₁₇ ~ C ₁₂ H ₂₅ , x is 0.05 to 0.15, y is 0.95 to 1.05, and z is 0.85 to 0.95. The polymer copolymer according to claim 24, wherein the ultraviolet (UV) absorption peak of the polymer copolymer in tetrahydrofuran (THF) solution is 430 nm (nm). The polymer copolymer according to claim 24, wherein the photo-excited fluorescence spectrum (PL) peak of the polymer copolymer in tetrahydrofuran (THF) solution is 611 nm (nm). The polymer copolymer according to claim 24, wherein the polymer copolymer has an ultraviolet (UV) absorption peak in the solid state of 430 nm (nm). The polymer copolymer according to claim 24, wherein the polymer-polymerized polymer has a photoexcitation fluorescence spectrum (PL) peak of 533 nm (nm) in a solid state. A method for preparing a high molecular polymer, comprising: preparing a bisbromobenzene compound, a bismuth borate compound, an aqueous potassium carbonate solution, and a toluene solution, and placing the solution in a nitrogen-containing reaction bottle; adding tetrakis(triphenylphosphine)palladium to the The reaction bottle is heated to a first predetermined temperature and refluxed for a first predetermined time, wherein the first predetermined temperature is 100 to 110 ° C, and the first predetermined time is 48 hours; the polymer is precipitated in a methanol solution and added Filtering and rinsing the high molecular polymer with a large amount of water; and heating the high molecular polymer to a second predetermined temperature under vacuum and drying for a second predetermined time, wherein the second predetermined temperature is 145 to 155 ° C, the second The scheduled time is 24 hours. A method for preparing a polymer copolymer comprising: preparing a bisbromobenzene compound, a bismuth borate compound, a dibromothiophene compound, an aqueous potassium carbonate solution, and a toluene solution, and placing the solution in a nitrogen-containing reaction bottle; adding tetrakis (triphenylbenzene) Palladium to the reaction flask and heated to a first predetermined temperature and refluxed for a first predetermined time, wherein the first predetermined temperature is 100-110 C, the first predetermined time is 48 hours; precipitation of the polymer copolymerization And filtering the polymer solution with a large amount of water; and heating the high molecular copolymer to a second predetermined temperature under vacuum and drying for a second predetermined time, wherein the second predetermined temperature is 145~155°C, this The second predetermined time is 24 hours.